Apparatus for converting hydrocarbon oils



June 19, 1945.

ATTORN EYS June 19, 1945. w. J. DEGNEN ET Al. f 2,378,394

APPARATUS FOR CONVERTING HYROCARBON OILS 5 Sheets-Shed 2 Filed May 31, 1940 lll-l.

ATTORNEYS June 19, 1945. w.'J. DEGNEN ET Al.

APPARATUS FOR CONVERTING HYDRGCARBON OILS Filed May 3l, 1940 3 Sheets-Shea?l 3 I :zizi- 12.1.2 D

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www A Mmm WHH B Patented June 19, 1945 APPARATUS HYDRO William J. Degnen,

Nelly, Jr., Houston, Jr., Peapack, N, Kellogg Company, tion of Delaware FOR (IlOIIVER'IINGr CARBON OILS Westfield, N.v J.,l J Tex., and Percival C.

Henry M. Keith,

assignors to The M. W.

Jersey City, N. J., a corpora- Application May si, 1940, serial No. 338,19e

' (ci. 19e-2) 3 Claims.

The present application is a. continuation-inpart of our co-pending application Serial No. 199,702 iiled April 2, 1938, now U. S, Patent 2,350,730.

Our invention relates to an apparatus for converting hydrocarbon oils and more particularly to a method for converting high boiling hydrocarbons into low boiling hydrocarbons, and apparatus capable of being used for converting high boiling` hydrocarbons into low boiling hydrocarbons or low boiling hydrocarbons into high boiling hydrocarbons in the presence of a catalyst.

'I'he catalytic cracking or polymerization of hydrocarbon oils is known lto ,the art. In general. the methods of the prior art consist in heating Figure 2 shows an embodiment of the revivifymg apparatus used in connection with that porhydrocarbon oil to cracking temperatures and4 passing highly heated oil or its vapors through a crackingl zone in the presence of. a suitabler catalyst in order to convert the hydrocarbon oil into the desired products. For various reasons, the catalyst passes through various stages of eiectiveness with use, eventually requiring regeneration. Thus, during an operation, the catalyst varies in effectiveness so that, for any given catalyst bed, only average effectivenessds obtained.

One object of ourl invention carrying out a method of revivied. h

Another object oi our invention is to provide a catalyst chamber in which the catalyst is continuously replaced.

Another object of catalyst chamber in oil vapors passing therethrough to control the temperature drop through the chamber.

A further object is the provision of means for sealing the catalyst chamber during the progressive movement of catalyst therethrough. kOther and further objects of our invention will appear from the following description.

In the accompanying drawings which form part of the instant specication and are to be read in conjunction therewith and in which like reference numerals are used to indicate like parts in the various views;

.Figure 1 is a diagrammatic view of a portion oi the apparatus embodying our invention.

our invention is to provide a is to provide an apparatus for cracking or polymerization in the Iis to provideA ous process, the catalytic polymerization in --which the catalyst is continuously removed and which heat is supplied to the .ber may tion of the apparatus shown in Figure 1.

Figure 3 is a sectional view of a catalyst contact chamber forming a portion` of the apparatus of our invention.

Figures: illustrates diagrammatic'ally arractionating system for the recovery and separation oi the cracked vaporous products.

In general, our invention contemplates the provision o! apparatus in which oil vapors to be converted are brought into contact with a catalyst in a conversion zone in which the catalyst is continuously being replaced so that the composition of the oil vapor leaving the catalyst chamber will be substantially constant and may flow directly to equipment without precautions being taken for change in its composition. This is a maior advantage over the intermittent processes of the prior art in which the products leaving the catalyst chamber may vary in composition. In an intermittent process, for example, in which hydrocarbon oils are cracked to form gasolinelike hydrocarbons, at' the beginning ci a cracking period the vapors leaving the reaction chamcontain from 40%"\to 50% oi gasoline. while, at the \end of the period, they may contain as low as 15% to 20% oi gasoline.

,In the intermittent processes, in order to obtain high crackingk per pass, the cracking period must nec be short due to the fact that the catalyst activity falls oi rapidly. In a continucracking per pass may be raised by increasing the circulation rate of the catalyst per unit of time.

In the intermittent processes, the oil vapors to be converted pass through the reaction chamber in contact with highly active catalyst only at or near the beginning of a cracking period. During the latter part of the period, the catalyst is progressively decreasing in activity. By the use of our apparatus continuous circulation of the catalyst in contact with the oil vapors is average composition oi the catalyst remains substantially constant and the oil vapor always contacts catalyst of highest activity at some point in the chamber.

Our apparatus further provides means whereby `the catalyst is continuously removed 'from the reaction chamber and is continuously revivified and recirculated to thecatalyst chamber.

Heat may be supplied to the reaction chamber to compensate for the loss of heat during the endothermic reaction of cracking. Il the, apparatus is to be used for polymerization, heat attained, the

yfluid through pipes |26 and |21.

may be removed from the catalyst .by a heat exchanging medium to remove the exothermic heat of polymerization; 4

We ywill describe our apparatus in connection with the cracking of hydrocarbon oils. It is to be understood, however, that our apparatus may be used for the conversion of light hydrocarbons into heavier hydrocarbons, as well as the conversion of heavy hydrocarbons into lighter Ihydrocarbons.

The hydrocarbons undergoing conversion, for example gas oil, are vaporized and heated to a suitable conversion temperature in heater and then introduced into the base of the catalyst chamber 39 through line 31 and branch line 38. For catalytic cracking this temperature may be in the range of about 750 to 1000 F. and preferably in an intermediate range of about 800 to 900 F. The hot vapors pass upward through the catalyst mass and are discharged from the chamber through line 45 to a suitable fractionating or separating system such as that illustrated diagrammatically in Figure 4, wherein the cracked vapors are separated into the desired fractions, such as normally gaseous hydrocarbons, motor fuel and recycle stock.

In the reaction chamber the heated vapors react to form lighter hydrocarbons in the presence of a catalyst. The catalyst in our apparatus is of a granular nature such that it can be fed to and Withdrawn from the reaction chamber 3! continuously. The fresh catalyst which may be used or catalyst material Iwhich has ,been revivied, is fed through conveyor |08 for passage through duct |09 into the catalyst feeding hopper y I0. The conveyor |08 is provided with any suitable conveying means driven by any suitable means such as an electric motor I l2. The feeding of the catalyst material ||3 from the feeding hopper is controlled 'by a cone type valve ||4, provided with hydraulic operating means I5. The catalyst material passes from ythe feeding hopper l0 through a duct l5 into a sealing hopper |l1, whence it is fed into the reaction chamber by a rotary bucket type valve or Star- Feeder ||8, operated by an electric motor ||9, through suitable gears |20- The used catalytic material is withdrawn from the reaction chamber 39 by a rotary buckettype valve or Star-Feeder |2| operated by an electric motor |22. The motors |20 and |22 may be synchronized so that the rate of feeding and the rate of withdrawal are kept the same. The used catalytic material passes into a sealing hopper |23, the discharge of which is controlled by a cone type valve |24, operated by a `hydraulic operating mechanism |25. The hydraulic operating mechanisms and |25 are adapted to be supplied with hydraulic A fluid pump |28 operated by an electric motor |29 supplies the fluid from pipe |30 for functioning the hydraulic operating mechanisms ||5 and |25. A timing control mechanism |3| of any suitable type known to the art controls the electric motor |29 and may also be connected to valves provided in lines |26 and |21 so that the cone type valves ||4 and |24 are intermittently operated to introduce fresh catalytic material into sealing hopper ||1 and to withdraw used catalytic material from sealing hopper |23. An inert gas, such as flue gas, steam, or a dry hydrocarbon gas from the fractionating system (not shown), if desired, under suitable pressure and at a suitable tempera-- ture, is introduced into manifold |32. A pipe |33, controlled by a valve |34, permits gas from manifold |32 to flow into ulpper sealing hopper ||0. The pressure of the gas is such that it is slightly in excess of that existing in the catalyst chamber. The imposition of this pressure in upper sealing hopper ||0 andlin feeding hopper ||1 will effectively prevent leakage outward of the cracked vapors. Any leakage which might occur will be into the reaction chamber 39. The capacity of the lower sealing hopper |35 is sufficiently greater than the discharge hopper |23 so that there lwill always be a quantity of material present in lower sealing hopper |35. Thus continuity of feed to the reviviiier is assured. The pressure in upper sealing. hopper ||0 may be readily controlled by valve |34 which may be automatically controlled by differential pressure controller between the upper sealing hopper ||0 and the reaction chamber, if desired.

Sealing gas from manifold |32 is also introduced through pipe |36 controlled by valve |31 into the discharge hopper |23. By control of valve |31, the pressure withindischarge hopper |23 is controlled to be slightly in excess of that which exists in pipe 31 and in the reaction chamber 39 so that the gas introduced into the discharge hopper |23 will denude and strip the catalytic material discharged of vapors which are carried either absorbed in the catalytic material or physically mixed in the mass. The stripped vapors and sealing gas will leave the discharge hopper |23 through pipe 40 which is controlled by valve 4| and pass through pipe 38 into the reaction chamber along with the hot vapors to be reacted in the reaction chamber.

The stripped, used catalyst passes into the lower sealing hopper |35, whence it passes through duct |31a and is fed :by conveyor |38 to the revivifying operation. Sealing gas from manifold |32 passes through the pipe |39 controlled by valve |40 into the lower sealing hopper |35 adapted to seal the lower end of the reaction chamber. If it is desired to locate the revivifier adjacent the reaction chamber, the used catalytic material may be withdrawn through duct |4| normally sealed by a cover plate |42.

Any desired rate of catalyst flow-may be obtained by controlling the speed of motors |20 and |22. The timing arrangement |3| is so controlled that cone type valves ||4 and |24 are operated with suflicient frequency to keep a supply of material in'feeding hopper ||1 and to keep the discharge hopper |23 suiliciently free of material to receive the used catalytic material flowing from the reaction chamber past valve |2l. It will be obvious, of course, that the conveyors will be operated at a synchronous speed to keep the upper sealing hopper ||0 supplied with material and maintain the material in the lower sealing hopper |35 at a safe operating level.

Referring now to Fig. 2, we show one embodiment of a revivifying apparatus capable of continuously revivifying the used catalytic material. Conveyor |38 provided with suitable conveying means |43 feeds the used catalytic material into a hopper |44, from which it is withdrawn through duct |45 and passed through a conveyor tube |46 by a feeding screw |41 operated by an electric motor |48. The conveyor tube |46 and the feeding screw |41 are tapered to cause the catalytic material to pack densely, enabling it, per se, to act as a seal. The pressure of the sealing gas in the discharge hopper |35 exists throughout the conveyor tube |38 and in feeding hopper |44, `so that any leakage will be r,merely of material inwardly toward the revivier. The revivifler is of the rotary kiln type in which the catalytic material is contacted with a gas which will effectively remove all or some of the carbon absorbed in the process and regenerate the catalyst to active condition. Producer gas reactions enabling a removal of carbon by reduction of carbon dioxide and steam may be employed, though We prefer to use simple oxidation with air.

In starting the operation of the revvier, air from the air manifold |49 passes through pipe |50 through valve |5|, to a burner |52, to which fuel gas is supplied through the pipe |53. The kiln shell |54 is provided with a ring gear |55 meshing with the pinion |56 which is driven by an electric motor |51, enabling lthe kiln to rotate upon its saddles |58 and |59, on suitable rollers |60. -End sections |6| and |62 are stationary.

After the revivier reaches a sufficient temperature, the burner |52 is shut off and valve |5| is closed. Valve |63 is opened and air under pressure is passed into the revivier in Contact with the used catalytic material. The resulting oxidation will burn the carbon and adsorbed compounds from the catalyst material, revivifyi ing it. The resulting products of combustion are Withdrawn from the revivier through duct |64 and pass through a centrifugal separator |65 for removal of entrained catalytic material dust, which is collected in the separator bottom |66 and removed therefrom by conveyor screw |61 operated by an electric motor |68.

The clean flue gases leave the separator |65 through duct |69 and may pass through duct |10 to the stack |1| by opening dampers `|12 and |13. The heat is the gases resulting from revivii'lcation of the catalyst may be recovered in partby passing them through a fiue gas steam generator |15, after which they may pass through duct |16, past damper |13 to the stack |1|. A portion of the cooled flue gases may be withdrawn through duct |18 by blower |19 and passed through duct |80 for recirculation to the revivier to control the temperature of the reviviiication.

A compressor |8| supplies air to the pipe |49 for passage to the revivier. A portion of the gases of revivification may be withdrawn through pipe |82 and `passed through cooler |83 for compression by compressor |84 and passage through pipe |85 to a sealing gas receiver |86. The cooler may be by-passed by by-pass pipe |81 controlled by valve |88. The compressed flue gases in the flue gas receiver acts as a source of sealing gas for the sealing gas system heretofore described. The sealing gas is withdrawn from the flue-gas receiver |86 through pipe |89 and may be passed, if desired, through a reheater |90 for heat exchange ,with a hot medium such as superheated steam or a portion of hot flue gas from duct |64, supplied to heat exchanger through pipe |9|. The sealing gas may by-pass the reheater |90 through pipe |92, controlled by valve |93. The sealing gas passes from the reheater |90 or from by-pass line |92 into the sealing gas manifold |32. The rotary revivifier is mounted at a slight angle, the stationary section |62 being lower than the stationary section |6I, so that the revivied catalytic material passes from the revivier through duct |94 into a discharge hopper |95. Fresh catalytic material may be added at this point from hopper |96 through duct |91 controlled by valves |98 and |98'. It will be noted that the revivifier may operate under pressure and valves |98 and |98 serve as locks in introducing fresh catalyst.

The catalytic material which is too ne for recycling is separated by maintaining the velocity of the regeneration gas circulated through the regenerator at such a value that the lines are suspended therein and subsequently separated in the separator |65. The revivied catalytic material from hopper is fed by screw conveyor |99, which is operated by electric motor 200, into conveyor feeding chamber 20|, from which the catalytic material passes through duct 202 to the fresh catalytic material conveyor tube |08 for carriage by conveyor means to the reaction chamber catalyst feeding hopper I0.

Referring now to Figure 3, we have shown a catalytic reaction chamber provided with means for continuously heating the reaction zone in order to compensate for the endothermic reaction of cracking. Catalyst is admitted by a valve 213, the catalyst passing into an upper compartment 214 formed within the reaction chamber 224 by a tube sheet 215 which acts as a distributing plate to distribute the catalyst 216 to the feeder tubes 211. 'Ihe arrangement is such that accumulations of stagnant catalyst adjacent the upper openings of the catalyst tubes 218 is avpided. The feeder tubes 211 extend some distance downwardly into the reaction tubes 218. Below the feeder tube sheet 215 we position a tube sheet 219 in which the catalyst tubes 218 are welded or rolled. The space 280 between the tube sheet 215 andthe tube sheet 219 serves as an inlet vapor space to which the incoming hot vapors to be cracked are introduced through pipe 22|. The feeder tubes 211 feed the catalyst to the catalyst tubes 218. The length of the feeder tubes will determine, the Vheight of the catalyst material maintained within the. catalyst tubes. By varying the length of the feeder tubes, the 'amount of catalyst in' the catalyst tubes is determined. This enables us to change the amount of catalyst for cracking various types of stock and employing different types of catalytic material.

The lower portions of the catalyst tubes" are welded or rolled in a lowerv tube sheet 28|. A plurality of baffles the exterior of catalyst tubes 218 transversely of the heating jacket229 to direct the flow of the heating medium which is introduced to the heating jacket through duct 228 and withdrawn therefrom through duct 230. Heat exchange between the heating medium and the reactants within the' catalyst tubes supplies heat to the endothermic cracking reaction.

In order toremove the catalyst and the vapors separately from the lower ends of the catalyst tubes, we provide means to effect the separation of the catalyst and the vapors. It will benoted that the catalystl tubes 218 extendbeyond the lower tube sheet 28|. To these extensions are tted elements comprising upper cylindrical portions 284 and lower conical portions 285. The cylindrical portions 284 are provided with slots 286, normally covered by screens.

The screens are made with a mesh sufliciently small to permit the discharge of the vapors while preventing the catalyst from passing therethrough.

A plurality of angles 294 are supported by a cross member 295 and are positioned beneath and adjacent discharge openings of cones 285. The cross member 295 is pivotally supported on links X296 and 291. The reciprocating rod 265, driven 282 and 283 are disposed around as indicated hereinabove, passes through a stuifing box and is adapted to actuate the gridwork formed by cross members 295 and angles 29|. The reciprocation of the grid alternately moves the angles clear of the respective discharge openings and to a position blocking the same. When the grid is clear of the openings, catalyst material will flow from the discharge cones 285 to the space 298 beneath the discharge arrangement. From the space 298 the catalyst material passes by valve 299 into the sealing hopper 300 from which it is discharged past valve 301. The sealing gas for the lower hopper is introduced through pipe 268,

The slots 286 in the base of the discharge cones are made considerably larger in total area than the internal cross sectional area of the tubes. As shown, the area of the slots is substantially four times as large as the internal cross sectional area of the tubes. This enables ready separation of the cracked vapors from the spent catalyst material to be effected. The discharge valves 299 and 30l and the catalyst feeding valve 213 are operated either by electrical or uid pres'- sure control mechanism in accordance with a time cycle regulated to introduce the catalyst at definite intervals in amounts proportioned according to the rate of catalyst ow from the tubes. A level gauge (not shown) may be ernployed in an upper feed compartment. A level gauge may be employed to indicate the amount of catalyst material in a lower discharge compartment. The change in levels of the upper and lower hoppers will serve to indicate the rate of catalyst ilow through the catalyst chamber.

By way of illustration and not by way of limitation, a Mid-Continent virgin gas oil was supplied as charging stock for the process. The catalytic materal was alumina deposited upon silica gel. The reaction temperature maintained within the catalyst bed varied from 840 F. at the bottom to 890 F. at the top. The time in which the catalyst was retained in passing through the chamber was about 8.25 hours. The space velocity during the operation was 4.28 barrels per hour of charge per ton of catalyst material in the bed.v Under these conditions the following yields were obtained:

Percent Gasoline (100% C4 recovery) -vo1 46 Cycle stock vo1 48 Gaswt 9 Coke wt 2.4

The catalyst was continuously revivified. The

gasoline yield from this run is approximately 12% greater than that predicted for a run under similar conditions made in a stationary catalyst bed.

The operation of our apparatus will be understood from the foregoing description. It will be seen that we have accomplished the objects of our invention. We have provided an apparatus for catalytic cracking whereby the composition of the oil vapor leaving the catalyst chamber may be maintained substantially constant. This enables it to flow directly to the fractionating and stabilization equipment without special precaution being taken for periodic changes in its composition. This is not true in the intermittent process in which the gasoline content of the vapors leaving the reaction chamber may vary from 40% to 50% at the start of the cracking period, and be as low as 15% to 20% at the end of the cracking-period.

. In order to obtain a very high cracking per pass in the intermittent process the cracking periods must necessarily be short due to the rapid falling off of catalyst activity. Through our means for continuous catalytic material replacement, the cracking per pass may be raised by circulating more catalyst per unit of time. In the intermittent process the vapors contact highly active catalytic material only a short period of time. In our apparatus highly active catalytic material is constantly being supplied so that there is always present in the reaction zone a considerable bed of highly active catalytic material.

Besides catalytic cracking, the apparatus is also suited to other endothermic catalytic reactions such as dehydrogenation of hydrocarbon oils and gases. To adapt the apparatus to exothermic reactions such as catalytic polymerization or synthesis reactions, provision would be made for removing excess heat produced during the reactions.

We have provided means for supplying the heat of reaction continuously during the cracking reaction,` to enable us to obtain a high percentage of cracking per pass. It is to be understood, of course, that if desired, a non-heated type of reaction chamber may be employed, and the heat supplied by high preheat of the cracked vapors.

It will be understood that certain features and subcombinations are of utility and may be employed without subcombinations. This is contemplated by and is within the scope of our claims. It is further obvious that various changes may be made in details within the scope of our claims without departing from the spirit of our invention. It is, therefore, to be understood that our invention is not to be limited to the specific details shown and described.

We claim:

1. Apparatus for continuous catalytic cracking of hydrocarbon oils comprising a pipe still for heating said oils ta a cracking temperature, a

cracking chamber provided with a granular catalyst inlet and a granular catalyst outlet and also provided with a charging stock' inlet and a cracked product outlet, said inlets and said outlets being positioned at opposite ends of said chamber, a transfer line connecting said charging stock inlet with said pipe still, a ractionating system, means for introducing productsfrom the cracked product outlet to said fractionating system, a revivification chamber provided with a granular catalyst inlet and a granular catalyst outlet and also with areviviflcation medium inlet and a reviviilcation medium outlet, said last-mentioned inlets and said last-mentioned outlets being positioned at opposite ends of said reviviiicationl chamber, means for transferring hot spent granular catalyst from said cracking chamber outlet to said revivication chamber inlet while the cracking and revivification operations are in progress, said means comprising a valve adapted to transfer granular catalyst, means for maintaining a zone of inert gas at a pressure higher than the pressure in the cracking chamber adjacent the down-stream side of said last-mentioned valve to prevent the escape'of reactant gas from said cracking chamber and means for transferring hot revivied granular catalyst from said reviviflcation chamber outlet to said cracking chamber inlet while the cracking and revivication oper ations are in progress, said last-mentioned means comprising at least one valve adapted to transfer granular catalyst and means for maintaining a zone of inert gas at a -pressure higher than the reference to other features and asvasca catalyst thereto, means for maintaining a zone of inert gas'at a pressure higher than the pressure in the cracking chamber on the 11p-stream side of said 1ast`mentioned valve to prevent the escape of reactant gas from said cracking chamber, means including a valve belowsaid chamber for maintaining said chamber substantially full of catalyst material and for discharging catalyst therefrom at substantially the rate at which itk is introduced thereto, meansk for continuously heating hydrocarbon vapors to acracking temperature and for passing said heated vapors through said chamber, a fractionating system,

- means for introducing products from said con- -version chamber to said fractionating system, a

catalyst regeneration chamber, means including the second-named valve below said conversion chamber for admitting spent catalyst from said conversion chamber to said regeneration cham-v ber, means for maintaining a zone of inert gas at a pressure higher than the pressure in the conversion chamber adjacent" the down-stream side of said last mentioned valve to prevent the escape of the reactant gas' from said conversion chamber, means for feeding granular catalyst disposed below the regeneration chamber for discharging regenerated catalyst therefrom at substantially the rate at which it is introduced thereto and means for returning regenerated 'catalyst discharged through said feeder means for introduction through said lnrst-named valve.

3. Apparatus for continuous catalytic cracking "of hydrocarbon oils comprising a pipe still for heating said oils to a cracking temperature, a cracking chamber provided with a catalyst inlet and a catalyst outlet and also provided with a charging stock inlet and a cracked product outlet, a transfer line connecting said charging stock inflet with'said pipe still, a fractionating system, means -for introducing products from the cracked product outlet to said fractionating system, a reviviflcation chamber provided with a catalyst inlet and a catalyst outlet and also with a revivification medium inlet and a revivication medium outlet, means for transferring hot spent catalyst from said cracking chamber outlet to said revivication chamber inlet while the cracking and revivification operations are in progress, said means comprising a valve adapted to transfer catalyst, means for maintaining a zone of inert gas at a pressure `higher than the pressure in the crackingchamber adjacent thedown-stream side of said last mentioned valve to prevent the escape of reactant gas from said cracking chamber', means for transferring hot revivifled catalyst from said revivication chamber outlet vt0 said cracking chamber inlet while the cracking` and reviviflcation operations are in progress, said last-mentioned means comprising at least one valve adapted to transfer catalyst, and means for maintaining a zone of inert gas at a pressure higher than the pressure in\ the cracking chamber on the up-stream vside of said last mentioned valve to prevent the escape of reactant gas from said cracking chamber.

WILLIAM J. DEGNEN.

,\ t Y M. NELLY, Ja.

- PER IVAL C. KEITHgJm 

